CN105278250B - Negative photosensitive resin composition - Google Patents
Negative photosensitive resin composition Download PDFInfo
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- CN105278250B CN105278250B CN201510111158.0A CN201510111158A CN105278250B CN 105278250 B CN105278250 B CN 105278250B CN 201510111158 A CN201510111158 A CN 201510111158A CN 105278250 B CN105278250 B CN 105278250B
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- siloxanyl monomers
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- 239000011342 resin composition Substances 0.000 title abstract 3
- -1 polysiloxane Polymers 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 46
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 125000005401 siloxanyl group Chemical group 0.000 claims description 26
- 150000008064 anhydrides Chemical group 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 150000002240 furans Chemical class 0.000 claims description 5
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 5
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical group C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical class ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 1
- WGOQTNXYTDSHRT-UHFFFAOYSA-N 9h-fluorene-1-carbonitrile Chemical class C1C2=CC=CC=C2C2=C1C(C#N)=CC=C2 WGOQTNXYTDSHRT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 125000004050 enoyl group Chemical group 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical group CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Materials For Photolithography (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a negative photosensitive resin composition, which comprises: (A)5 to 25 weight percent of a polysiloxane compound; (B)0.1 to 20 weight percent silicate oligomer, (C)0.1 to 10 weight percent photoacid generator; and (D) the balance solvent. The negative photosensitive resin composition provided by the invention has excellent characteristics such as high heat resistance, high transparency, high chemical resistance and high moisture resistance.
Description
Technical field
The present invention relates to a kind of negative light-sensitive resin combinations, more particularly, to a kind of minus suitable for high-temperature technology
Photosensitive polymer combination.
Background technique
In the preparation process of display panel and touch panel, always with the various photoresist groups such as eurymeric or minus
Object is closed as material, and is patterned and hardened these resin combinations using its photobehavior to form passivation layer, protect
The components such as sheath or insulating layer.
In view of the transparency conducting layer (such as tin indium oxide, ITO) as panel member be required must to reach high transparency with
The property of high conductivity, therefore the temperature in sputter ITO also needs higher and higher, universal sputter temperature has been up to 280 DEG C at present,
And it is used to also need to bear high temperature in the process as components such as protective layer or passivation layers.However, currently known with acrylic acid tree
Photosensitive polymer combination based on rouge or silicone resin generates serious Yellowing in high-temperature technology, and causes this
The contraction of resin combination volume, and then lead to problems such as adaptation in display panel or touch panel bad.In addition, well known
The components such as protective layer or passivation layer are also required to be promoted for the anti-etching property of the etching solution of ITO etc., to ensure ITO layer or metal
The adherence of orientation, therefore the work of the display panel or touch panel in the ITO with high transparency and highly conductive characteristic can not be applied
In skill.
Therefore, need a kind of novel negative light-sensitive resin combination at present, with high-fire resistance, high transparency,
The excellent characteristics such as high chemical resistance and high moisture-proof, to be applied to the ITO high temperature work with high transparency and highly conductive characteristic
In skill.
Summary of the invention
The main purpose of the present invention is to provide a kind of negative light-sensitive resin combinations, and can pass through the height of the composition
The characteristics such as heat resistance, high transparency, high endurance and high moisture-proof, and then be applied in high-temperature technology to provide display surface
The components such as passivation layer, protective layer or insulating layer in plate or touch panel.
To reach above-mentioned purpose, negative light-sensitive resin combination provided by the present invention can include: (A) 5 to 25 weight
The polysiloxane compound of percentage, is polymerized by various of monomer, wherein these monomers can include at least: just like formula (a-
1) siloxanyl monomers shown in and the siloxanyl monomers containing anhydride group；
Wherein, R1It is each independently C1-6Alkyl；
(B) the silicic acid ester oligomer of 0.1 to 20 weight percent, as shown in formula (b-1)；
Wherein, R2It is each independently C1-6Alkyl；And the integer that n is 2 to 10；
(C) photoacid generator of 0.1 to 10 weight percent；And
(D) balance solvent.
In the negative light-sensitive resin combination provided by aforementioned present invention, (A) polysiloxane compound is as tree
The main component of oil/fat composition, and be used to polymerize in the monomer of (A) polysiloxane compound, the siloxanes as shown in formula (a-1)
Monomer includes the alkoxy of four connections on the silicon atoms, it is possible to provide the crosslinking points of condensation polymerization each other, and this contains anhydride group
Siloxanyl monomers in, anhydride group can promote development solubility.In addition, by caused by exposure (C) photoacid generator
Acid, can further such that (A) polysiloxane compound carry out condensation reaction, to improve the crosslink density of its resin combination, by
This improves its heat resistance.Furthermore in order to increase the chemical resistance of negative light-sensitive resin combination of the invention (such as
The elching resistant of ITO etching solution), the present invention is that (B) silicic acid ester oligomer is provided in the resin combination as crosslinking agent,
Generated acid when being exposed by (C) photoacid generator, is further crosslinked, to reach more with (A) polysiloxane compound
Big crosslink density.
In (A) polysiloxane compound of the negative light-sensitive resin combination of aforementioned present invention, this contains anhydride group
Siloxanyl monomers can be as shown in formula (a-2):
Wherein, R3It can be selected from by being directly bonded, C1-6Alkyl and C1-6Group composed by alkoxy；R4For C1-6Alcoxyl
Base；And R5It is each independently C1-6Alkyl or C1-6Alkoxy.
In such as above-mentioned negative light-sensitive resin combination, in siloxanyl monomers shown in formula (a-1), R1It preferably can be with
For C1-3Alkyl, and most preferably tetraethoxysilane.Furthermore this contains the siloxanes of anhydride group as shown in formula (a-2)
In monomer, R3Preferably C2-4Alkyl, wherein with C3Alkyl be more preferable；R4And R5Preferably C1-3Alkoxy, wherein
The siloxanyl monomers for containing anhydride group as shown in formula (a-2) are most preferably dihydro -3- [3- (triethoxy silicon substrate) propyl]
Furans -2,5- diketone.
In addition, the total weight ratio of (A) polysiloxane compound is accounted for based on these monomers, siloxanes list shown in formula (a-1)
Body can account for 5 to 60%；And the siloxanyl monomers for containing anhydride group can account for 0.1 to 40%.
As in above-mentioned negative light-sensitive resin combination, (A) polysiloxane compound may also include at least just like formula (a-
3) siloxanyl monomers shown in,
Wherein, R6For hydrogen or C1-20Non-hydrolyzable organic group, the C1-20Non-hydrolyzable organic group for example can be
C1-20Linear chain or branched chain alkyl, C1-20Linear chain or branched chain alkenyl, C1-20Aryl or its similar to substituent group etc., in addition,
The above-mentioned non-hydrolyzable organic group can be substituted or be unsubstituted, for example, can be for through halogen, epoxy group, amido, methyl-prop
The substituent groups such as enoyl-, cyano, fluorenes or vinyl replace, however R6It is not limited to this；And R7Be each independently selected from by
C1-6Group composed by alkoxy and aryloxy group.For example, monomer shown in formula (a-3) can be methyltrimethoxysilane, first
Ethyl triethoxy silicane alkane, three isopropoxy silane of methyl, three n-butoxy silane of methyl, ethyl trimethoxy silane, ethyl three
Ethoxysilane, three isopropoxy silane of ethyl, three n-butoxy silane of ethyl, n-propyl trimethoxy silane, n-propyl three
Ethoxysilane, n-butyltrimethoxysilane, ne-butyltriethoxysilaneand, n-hexyl trimethoxy silane, n-hexyl three
Ethoxysilane, phenyltrimethoxysila,e or phenyl triethoxysilane.
Wherein, (A) polysiloxane compound as the siloxanyl monomers as shown in formula (a-1), this contain the silicon oxygen of anhydride group
Alkane monomer is at least polymerized just like siloxanyl monomers shown in formula (a-3), wherein accounts for (A) polysiloxanes based on these monomers
The total weight ratio of compound, siloxanyl monomers shown in formula (a-1) account for 10 to the 60%, siloxanyl monomers for containing anhydride group and account for
0.5 to 40% and 0 to 80% at least is accounted for just like siloxanyl monomers shown in formula (a-3).
And in the siloxanyl monomers as shown in formula (a-3), R6Preferably C1-3Alkyl or phenyl；And R7It is preferred that respectively independent
Ground is selected from by C1-3Alkoxy, wherein the siloxanyl monomers as shown in formula (a-3) more preferably can be at least one selected from by
Composed by phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxysilane and ethyl triethoxysilane
Group.
In addition, the molecular weight of above-mentioned (A) polysiloxane compound can be 1000~6000 grams/mol, preferably 1500
~4500 grams/mol.
Furthermore the resin combination according to provided by this case, wherein in the silicic acid ester oligomer shown in formula (b-1), R2
Preferably C1-3Alkyl, and be wherein more preferable with methyl silicate.
In addition, the resin combination according to provided by this case, wherein (C) photoacid generator can provide proton after exposure,
For example, it can be trichloromethyl-s-triazine class, Diaryl iodonium salt, triarylsulfonium salt etc., and wherein preferably can be three
Phenyl sulfonium salt, in triphenyl sulfonium salt, and preferably can for as formula (c-1) into formula (c-3) it is any shown in triphenyl sulfonium salt:
Negative light-sensitive resin combination provided by the present invention can be used as the transparent photoresist of new generation insulating layer,
With the transparency, metal base adherence after high temperature resistant, good, low exposure energy, Yi Xianying and moisture-proof, etch resistant etc. are good for it
Characteristic can be applied to have in high transparency and the ITO high-temperature technology of highly conductive characteristic.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
It is bright to be described in further detail.
The preparation of preparation example 1- polysiloxane compound A-1
Take 83.2 grams of tetraethoxysilane, 40.92 grams of methyltrimethoxysilane, 30.44 grams of dihydro -3- [3-
(triethoxy silicon substrate) propyl] diacetone of furans -2,5- diketone and 39.66 grams of phenyltrimethoxysila,e at 172 grams
It is stirred in alcohol (DAA) solvent, slowly instills 54 grams of phosphate aqueous solution (0.0092 gram of H3PO4It is dissolved in 54 grams of water) after, heating
To 110 DEG C of one condensation polymerization reactions of progress, the reaction time is 2 hours.After the reaction was completed, alcohol and water are removed using distillation mode,
The solid content of resulting polysiloxane compound A-1 is 45%, and molecular weight is 3800 grams/mol.
The preparation of preparation example 2- polysiloxane compound A-2
Take 52.0 grams of tetraethoxysilane, 13.64 grams of methyltrimethoxysilane, 15.22 grams of dihydro -3- [3-
(triethoxy silicon substrate) propyl] dipropyl of furans -2,5- diketone and 118.98 grams of phenyltrimethoxysila,e at 172 grams
It is stirred in keto-alcohol (DAA) solvent, slowly instills 54 grams of phosphate aqueous solution (0.0092 gram of H3PO4It is dissolved in 54 grams of water) after, it rises
For temperature to 110 DEG C of one condensation polymerization reactions of progress, the reaction time is 2 hours.After the reaction was completed, using distillation mode remove alcohol with
Water, the solid content of resulting polysiloxane compound A-2 are 45%, and molecular weight is 2000 grams/mol.
The preparation of preparation example 3- polysiloxane compound A-3
This preparation example is generally identical as above-mentioned preparation example 2, the difference is that, four ethoxies are not used in this preparation example
Base silane uses 47.66 grams of methyltrimethoxysilane, 15.22 grams of dihydro -3- [3- as the monomer in synthesis
(triethoxy silicon substrate) propyl] PGMEA of furans -2,5- diketone and 118.98 grams of phenyltrimethoxysila,e at 172 grams
It is stirred in solvent, slowly instills 54 grams of phosphate aqueous solution (0.0092 gram of H3PO4It is dissolved in 54 grams of water) after, it is warming up to 110 DEG C
A condensation polymerization reaction is carried out, the reaction time is 2 hours.After the reaction was completed, alcohol and water are removed using distillation mode, it is resulting poly-
The solid content of silicone compounds A-3 is 45%, and molecular weight is 2500 grams/mol.
Embodiment 1-6
Table 1 is please referred to, by polysiloxane compound, silicic acid ester oligomer, photoacid generator and solvent according to 1 institute of table
The compositing formula shown is configured to the photosensitive polymer combination of embodiment 1 to 6, wherein used polysiloxane compound is
Polysiloxane compound A-1 and A-2 as prepared by above-mentioned preparation example 1-2.Used silicic acid ester oligomer is methyl silicate.
And the photoacid generator used is Omnicat 432, Irgacure 290 and TR-PAG-201, these photoacid generators are all three
Phenyl sulfonium salt, corresponding chemical formula are as follows:
Table 1 (unit: gram)
Comparative example 1-6
Table 2 is please referred to, by polysiloxane compound, silicic acid ester oligomer, photoacid generator and solvent etc. according to shown in table 2
Compositing formula be configured to the photosensitive polymer combination of comparative example 1 to 6, wherein used polysiloxane compound is served as reasons
Polysiloxane compound A-1 to A-3 prepared by above-mentioned preparation example 2-3.In a comparative example using other type of crosslinking agent to take
For silicic acid ester oligomer used in the present invention, wherein these crosslinking agents used are three (3- (trimethoxy silicon substrate) propyl)
Isocyanuric acid ester (Tris (3- (trimethoxysilyl) propyl) isocyanurate, A-Link 597), bis- (three ethoxies
Base silicyl) ethane (Bis (triethoxysilyl) ethane, SIB 1817), PSI-021 (Poly
(diethyoxysiloxane) 20.5-21.5%Si, 40-42%SiO2) and PSI-023 (Poly
(diethyoxysiloxane) 23.0-23.5%Si, 48-52%SiO2)。
Table 2 (unit: gram)
Comparative example 7
This comparative example uses forever that photochemistry EOC 210 is as photosensitive polymer combination, by styrene, metering system
Acid,Benzyl methacrylate, the acrylic monomers such as tricyclodecyl, the polyacrylic acid resin obtained after aggregated condensation.
Test example
Firstly, preparing a substrate, and the substrate surface is cleaned with deionized water and acetone.Then, by above-described embodiment 1 to
6, negative light-sensitive resin combination prepared by comparative example 1 to 7 distinguishes even spread on the substrate in a manner of rotary coating.
Then, soft 5 minutes roasting at 90 DEG C, and a light shield is used, directly with extra-high-pressure mercury vapour lamp (exposure energy: 200mJ/cm2) right
The above-mentioned negative light-sensitive resin combination for being coated on substrate surface is exposed.Then, developed with 80 developer solution of ENPD
60 seconds.At 230 DEG C, 30 minutes hard bakings are carried out.Finally, with secondary water cleaning base plate and the photoresist layer at 25 DEG C, thus
Sample needed for obtaining.
<hardness>
Sample obtained by above-mentioned test example is to test to survey according to the 8.4.1 pencil scratch hardness of JIS K-5400-1990
The pencil hardness of fixed resulting sample.The measurement of hardness is using pencil hardness as unit, and the results are shown in Table 3.
<penetration after heat-resisting>
Sample obtained by above-mentioned test example heats 1 hour in the environment of 280 DEG C, after heat treatment, utilizes Photal
MCPD-3000 (big tomb science and technology) tests the penetration that these samples are 400nm for wavelength.The results are shown in Table 3 for it.
<water-fastness test>
Sample obtained by above-mentioned test example vibrates 30 minutes in 25 DEG C of ultrasonic sink.The assessment of water-fastness test
The results are shown in Table 3, wherein the assessment of water-fastness test are as follows: excellent 4B > 3B > 2B > 1B > 0B is bad.
<etch resistant test>
Sample obtained by above-mentioned test example is dipped in FeCl at 40 DEG C3In last 120 seconds.The test of its etch resistant is commented
Estimate that the results are shown in Table 3.Wherein, the assessment of etch resistant test are as follows: excellent 4B > 3B > 2B > 1B > 0B is bad.
Table 3
<resistance to heat shrinkage film rate and xanthochromia>
By in above-mentioned test example, the sample as prepared by embodiment 1 and comparative example 7 is heat-treated 1 hour at 280 DEG C,
And calculate its resistance to heat shrinkage film rate, wherein resistance to heat shrinkage film rate=(cephacoria of the resistance to Thermal test thickness-caudacoria of resistance to Thermal test is thick)/resistance to Thermal test
Preceding film thickness × 100%.And the evaluation criteria of visual xanthochromia are as follows: 3 > of transparent 5 >, 4 >, 2 > 1 is yellow.Its test result such as 4 institute of table
Show.
Table 4
By the result of table 4 it can be confirmed that negative light-sensitive resin combination provided by the present invention has the heat-resisting spy of height
Property, the heat-resistant quality of the insulating layer or protective layer that are known as panel can be significantly improved.
By above test result, it is expressly understood that negative light-sensitive resin combination provided by the present invention can be used as
The transparent photoresist of new generation insulating layer for example can be applied to touch panel insulating layer (OC1) and protective layer
(OC2) on, which has the good transparency after high temperature resistant, metal base adherence, low exposure energy, Yi Xianying and moisture-proof, resistance to
The good characteristics such as etching.
It is only for the sake of illustration for above-described embodiment, and the interest field that the present invention is advocated certainly should be with application
Subject to described in the scope of the patents, not just the above examples.
Claims (10)
1. a kind of negative light-sensitive resin combination, comprising:
(A) polysiloxane compound of 5 to 25 weight percent, is polymerized by various of monomer, wherein these monomers are at least
It include: just like siloxanyl monomers shown in formula (a-1), the siloxanyl monomers containing anhydride group, and at least just like formula (a-3)
Shown in siloxanyl monomers；
Wherein, R1It is each independently C1-6Alkyl；
Wherein, R6For C1-20Non-hydrolyzable organic group；And
R7It is each independently selected from by C1-6Group composed by alkoxy and aryloxy group；
(B) the silicic acid ester oligomer of 0.1 to 20 weight percent, as shown in formula (b-1)；
Wherein, R2It is each independently C1-6Alkyl；And
The integer that n is 2 to 10；
(C) photoacid generator of 0.1 to 10 weight percent；And
(D) balance solvent.
2. resin combination as described in claim 1, wherein in (A) polysiloxane compound, this contains anhydride group
Shown in siloxanyl monomers such as formula (a-2):
Wherein, R3Selected from by being directly bonded, C1-6Alkylidene and C1-6Group composed by alkylene oxide group；
R4For C1-6Alkoxy；And
R5It is each independently C1-6Alkyl or C1-6Alkoxy.
3. resin combination as described in claim 1, wherein (A) polysiloxane compound is as the silicon oxygen as shown in formula (a-1)
Alkane monomer and the siloxanyl monomers for containing anhydride group are polymerized, and account for the total of (A) polysiloxane compound based on these monomers
Weight ratio, siloxanyl monomers shown in formula (a-1) account for 5 to 60%；And the siloxanyl monomers for containing anhydride group account for 0.1 to
40%.
4. resin combination as described in claim 1, wherein (A) polysiloxane compound is as the silicon oxygen as shown in formula (a-1)
Alkane monomer, this contains the siloxanyl monomers of anhydride group, is at least polymerized just like siloxanyl monomers shown in formula (a-3), wherein
Account for the total weight ratio of (A) polysiloxane compound based on these monomers, siloxanyl monomers shown in formula (a-1) account for 10 to 60%,
The siloxanyl monomers containing anhydride group account for 0.5 to 40%, and at least just like siloxanyl monomers shown in formula (a-3) account for 0 to
80%.
5. resin combination as described in claim 1, wherein in (A) polysiloxane compound, the silicon as shown in (a-1)
Oxygen alkane monomer is tetraethoxysilane.
6. resin combination as claimed in claim 2, wherein this contains the siloxanyl monomers of anhydride group shown in formula (a-2)
For dihydro -3- [3- (triethoxy silicon substrate) propyl] furans -2,5- diketone.
7. resin combination as described in claim 1, wherein the silicic acid ester oligomer shown in formula (b-1) is methyl silicate.
8. resin combination as described in claim 1, wherein (C) photoacid generator is a triphenyl sulfonium salt.
9. resin combination as claimed in claim 8, wherein (C) triphenyl sulfonium salt is such as formula (c-1) to (c-3) any institute
The triphenyl sulfonium salt shown:
10. resin combination as described in claim 1, wherein the molecular weight of (A) polysiloxane compound is 1000~6000
Gram/mol.
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| CN111443573B (en) * | 2019-01-16 | 2023-06-06 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
| CN111443574B (en) * | 2019-01-16 | 2023-02-17 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
| CN111913355A (en) * | 2019-05-09 | 2020-11-10 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
| TWI735015B (en) * | 2019-07-30 | 2021-08-01 | 長興材料工業股份有限公司 | Polysiloxane resin, coating composition containing the same and application thereof |
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